Why are the IR-Active Frequencies Wrong in MOLPRO 2000.1? (fwd)
H.-J. Werner
werner at tc2.theochem.uni-stuttgart.de
Fri Dec 22 13:51:49 GMT 2000
The likely reason is that by default Molpro uses spherical harmonics,
while Gaussian uses cartesian basis functions (d,f,g..). Please add
the keyword CARTESIAN to your input (e.g., before basis) and try the
calculation again. Make sure that you get the same number of basis functions
in Gaussian and Molpro and an identical initial scf energy.
Should you still get unexpected results, please let me know.
H.-J. Werner
>
> Dear MOLPRO experts,
>
> I am using MOLPRO 2000.1. As a test of frequency calculations of
> heavy-element systems, I tried to repeat the frequency calculation of UF6
> published in J. Chem. Phys. 1998, 109, 3875-3881 (Hay & Martin). While I
> can get the same optimized structure and RHF energy as the literature data,
> the calculated frequencies for the IR-active modes are all wrong, but those
> for the Raman and other modes are actually the same as in the literature.
> I also have this problem for some other molecules.
>
> I am attaching here the input file and some simple output of UF6. I would
> appreciate it very much if any of you could let me know whether this is a
> bug of the code or my input file is actually wrong? Thanks.
>
> Merry Christmas to all,
>
>
> Jun Li
>
> --------input file-----------------
> ***, MOLPRO 2000.02 Calculations of UF6
> memory 50, m
> geomtyp=xyz
> geometry={
> 7 ! Number of Atoms
> example of cartesian XYZ coordinate input for MOLPRO
> U 0.0 0.0 0.0
> F 1.99 0.0 0.0
> F -1.99 0.0 0.0
> F 0.0 1.99 0.0
> F 0.0 -1.99 0.0
> F 0.0 0.0 1.99
> F 0.0 0.0 -1.99
> }
>
> basis={
> ! URANIUM LANL2DZ (6S,5P,2D,2F) -> [3S,3P,2D,2F]
> s,U, 0.244400000E+01,0.143300000E+01,0.667700000E+00,0.255600000E+00,
>
> 0.244400000E+01,0.143300000E+01,0.667700000E+00,0.255600000E+00,0.120000000E
> +00,0.400000000E-01
> c,1.4, 0.280278000E+00,-0.132311000E+01, 0.139499900E+01, 0.453123000E+00
> c,5.9, -0.837540000E-01,
> 0.608236000E+00,-0.818433000E+00,-0.905753000E+00, 0.123402000E+01
> c,10.10, 0.100000000E+01
> p,U, 0.113800000E+01,0.687400000E+00,0.250600000E+00,
>
> 0.113800000E+01,0.687400000E+00,0.250600000E+00,0.120000000E+00,0.400000000E-01
> c,1.3, -0.558150000E+00, 0.970172000E+00, 0.541903000E+00
> c,4.7, 0.225763000E+00,-0.420469000E+00,-0.545903000E+00, 0.742936000E+00
> c,8.8, 0.100000000E+01
> d,U ,0.382600000E+00,0.147300000E+00
> c,1.1, 0.100000000E+01
> c,2.2, 0.100000000E+01
> f,U ,0.411300000E+01,0.169700000E+01,0.677400000E+00,0.251000000E+00
> c,1.2, 0.218993000E+00, 0.459539000E+00
> c,3.4, 0.421699000E+00, 0.179066000E+00
>
> ! LANL2DZ Effective Core Potentials
> ECP,u ,78,4;
> 7; ! g potential
> 0, 4.51627250,-.22527100;
> 1, 368.687695,-53.780570;
> 2, 112.757671,-516.30521;
> 2, 30.2032915,-202.67382;
> 2, 10.2978355,-62.564405;
> 2, 3.49105150,-21.558956;
> 2, 1.26683910,-1.5390545;
> 8; ! s-g potential
> 0, 257.352944,2.61188160;
> 1, 83.1605428,81.2356657;
> 2, 29.7200513,353.246536;
> 2, 6.24821320,311.929223;
> 2, 4.16346720,-423.55258;
> 2, 3.00015110,293.216084;
> 2, 1.56000000,-21.344255;
> 2,0.870000000,1.66925480;
> 8; ! p-g potential
> 0, 288.729825,1.84143880;
> 1, 76.7838420,75.7054755;
> 2, 24.8252003,288.460167;
> 2, 5.12487350,250.728943;
> 2, 3.76033000,-318.89681;
> 2, 2.97617060,160.084492;
> 2, 1.99190170,33.7801891;
> 2,0.973883200,-2.0699997;
> 6; ! d-g potential
> 0, 350.469941,2.90820640;
> 1, 166.709130,74.3577628;
> 2, 85.8206119,587.114033;
> 2, 26.9842255,317.254368;
> 2, 7.15655920,102.842212;
> 2, 1.28408550,22.4214278;
> 7; ! f-g potential
> 0, 251.267075,3.93503390;
> 1, 108.010922,64.9434120;
> 2, 114.802189,265.180478;
> 2, 39.9112545,389.428409;
> 2, 11.9039784,153.476722;
> 2, 3.38507720,12.0807444;
> 2, 1.26776070,-1.3510138;
>
> spd, F, 6-31g*; c
> }
>
> gprint, basis, orbitals
> rhf
> print 3, 0
>
> optg;
>
> frequencies;
> thermo sym=Oh;
> print thermo;
> ---
>
> --------output-----------------
>
> 1 2 3 4
> 5
> Wavenumbers [cm-1] 217.27 217.27 217.27 260.70
> 260.70
> Intensities [km/mol] .00 .00 .00 26.08
> 26.08
> Intensities [relative] .00 .00 .00 2.82
> 2.82
> 6 7 8 9
> 10
> Wavenumbers [cm-1] 260.70 582.65 582.65 760.67
> 1043.98
> Intensities [km/mol] 26.08 .00 .00 .00
> 926.07
> Intensities [relative] 2.82 .00 .00 .00
> 100.00
> 11 12
> Wavenumbers [cm-1] 1043.98 1043.98
> Intensities [km/mol] 926.07 926.07
> Intensities [relative] 100.00 100.00
>
> Normal Modes of imaginary frequencies
> 1 2 3
> Wavenumbers [cm-1] 2.61 2.34 2.05
> Intensities [km/mol] .00 .00 .00
> Intensities [relative] .00 .00 .00
>
> Normal Modes of low/zero frequencies
> 1 2 3 4
> 5
> Wavenumbers [cm-1] 22.91 22.91 22.91 157.49
> 157.49
> Intensities [km/mol] .00 .00 .00 .00
> .00
> Intensities [relative] .00 .00 .00 .00
> .00
> 6
> Wavenumbers [cm-1] 157.49
> Intensities [km/mol] .00
> Intensities [relative] .00
>
>
>
> The published Gaussian results are: 157(t2u), 216(t2g), 209(t1u), 702(t1u),
> 582(eg), 761(a1g), where the T1u modes are IR-active. The MOLPRO IR
> freqeuncies listed above are 261 and 1043 cm-1 (comparing with 209 and 702
> cm-1)!
> *******************************************************
> Department of Chemistry Tel: (614)292-5227 (Office)
> The Ohio State University (614)529-7104 (Home)
> 100 West 18th Avenue Fax: (614)292-1685
> Columbus, Ohio 43210-1173 E-Mail: li.208 at osu.edu
> USA
> Homepage: http://chemistry.ohio-state.edu/~junli
> ********************************************************
>
--
Prof. Hans-Joachim Werner
Institute for Theoretical Chemistry
University of Stuttgart
Pfaffenwaldring 55
D-70569 Stuttgart
Tel: (0049) 711 / 685 4400
Fax: (0049) 711 / 685 4442
email: werner at theochem.uni-stuttgart.de
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